The invention relates to novel substituted aromatic thiocarboxamides, to processes for their preparation and to their use as herbicides.
It is already known that certain aromatic carbothioamides, for example 2,6-dichloro-benzothioamide (xe2x80x9cchlorthiamidxe2x80x9d), possess herbicidal properties (cf. GB-B 987253). However, the activity of this previously known compound, especially at low application rates and concentrations, is not entirely satisfactory in all areas of application.
The novel substituted aromatic thiocarboxamides have now been found of the general formula (I) 
in which
R1 represents hydrogen or halogen,
R2 represents the following group
xe2x80x94A1xe2x80x94A2xe2x80x94A3
xe2x80x83in which
A1 represents a single bond, or represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the group xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl,
A1 additionally represents in each case optionally substituted alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or arenediyl,
A2 represents a single bond, or represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the group xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, aryl, alkoxy, alkylsulphonyl or arylsulphonyl,
A2 additionally represents in each case optionally substituted alkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or arenediyl,
A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy, arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy or heterocyclylalkoxycarbonyl,
R3 represents hydrogen or halogen or together with R2 represents an alkanediyl or an alkenediyl group which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an SO2 group, an NH group, an N-alkyl group, a carbonyl group and/or a thiocarbonyl group, and
Z represents in each case optionally substituted monocyclic or bicyclic, saturated or unsaturated heterocyclyl, heterocyclylamino or heterocyclylimino.
The novel substituted aromatic thiocarboxamides of the general formula (I) are obtained if substituted aromatic nitriles of the general formula (II) 
in which
R1, R2, R3 and Z have the meanings given above are reacted with hydrogen sulphide (H2S) or with thioacetamide, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.
The novel substituted aromatic thiocarboxamides of the general formula (I) are notable for strong and selective herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkinylxe2x80x94alone or in conjunction with heteroatoms, such as in alkoxy, alkylthio or alkylaminoxe2x80x94are each straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially fluorine or chlorine.
The invention preferably relates to compounds of the formula (I) in which
R1 represents hydrogen, fluorine, chlorine or bromine,
R2 represents the following group
xe2x80x94A1xe2x80x94A2xe2x80x94A3
xe2x80x83in which
A1 represents a single bond, or represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the group xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl,
A1 additionally represents in each case optionally fluorine- or chlorine-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A2 represents a single bond, or represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94or the group xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl,
A2 additionally represents in each case optionally fluorine- or chlorine-substituted C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene,
A3 represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen, or represents in each case optionally halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups, or represents in each case optionally halogen-, cyano-, carboxyl-, C1-C4-alkyl- and/or C1-C4-alkoxy-carbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or represents in each case optionally nitro-, cyano-, carboxyl-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkyloxy-, C1-C4-halogenoalkyloxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl or phenyl-C1-C4-alkoxycarbonyl, (in each case optionally totally or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl-C1-C4-alkyl, isoxazole-C1-C4-alkyl, thiazole-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy or furylmethoxy, or represents perhydropyranylmethoxy or pyridylmethoxy,
R3 represents hydrogen, fluorine, chlorine or bromine or together with R2 represents an alkanediyl or alkenediyl group having in each case up to 4 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an SO2 group, an NH group, an Nxe2x80x94C1-C4-alkyl group, a carbonyl group and/or a thiocarbonyl group, and
Z represents in each case monocyclic or bicyclic, saturated or unsaturated heterocyclyl, heterocyclylamino or heterocyclylimino having in each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen atom or sulphur atom and/or optionally up to three groups from the series xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, xe2x80x94SOxe2x80x94 and/or SO2xe2x80x94, and which is optionally substituted by one or more groups from the series nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, C1-C6-alkyl (which is optionally substituted by halogen or C1-C4-alkoxy), C2-C6-alkenyl or C2-C6-alkinyl (which are in each case optionally substituted by halogen), C1-C6-alkoxy or C1-C6-alkoxy-carbonyl (which are in each case optionally substituted by halogen or C1-C4-alkoxy), C2-C6-alkenyloxy or C2-C6-alkinyloxy (which are in each case optionally substituted by halogen), C1-C6-alkylthio, C2-C6-alkenylthio or C2-C6-alkinylthio (which are in each case optionally substituted by halogen), C1-C6-alkylamino or di-(C1-C4-alkyl)-amino, C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl (which are in each case optionally substituted by halogen and/or C1-C4-alkyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl or phenylamino (which are in each case optionally substituted by nitro, cyano, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxycarbonyl).
The invention particularly relates to compounds of the formula (I) in which
R1 represents hydrogen, fluorine or chlorine,
R2 represents the following group
xe2x80x94A1xe2x80x94A2xe2x80x94A3
xe2x80x83in which
A1 represents a single bond, or represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the group xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl,
A1 additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A2 represents a single bond, or represents oxygen, sulphur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the group xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl,
A2 additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, or represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, or represents in each case optionally fluorine- or chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, or represents in each case optionally fluorine-, chlorine-, cyano-, carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, or represents in each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, (in each case optionally completely or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolemethyl, thiazolmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy,
R3 represents hydrogen, fluorine or chlorine or together with R2 represents an alkanediyl or alkenediyl group having in each case 1 to 3 carbon atoms which optionally contains at the beginning (or end) or within the hydrocarbon chain an oxygen atom, a sulphur atom, an NH group, an N-methyl group, a carbonyl group and/or a thiocarbonyl group, and
Z represents in each case monocyclic or bicyclic, saturated or unsaturated heterocyclyl, heterocyclylamino or heterocyclylimino having in each case 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen atom or sulphur atom and/or optionally up to two groups from the series xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, xe2x80x94SOxe2x80x94, and/or SO2xe2x80x94, and which is optionally substituted by one or more groups from the series nitro, hydroxyl, amino, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which are optionally substituted by fluorine, chlorine, methoxy or ethoxy); propenyl, butenyl, propinyl or butinyl (which are in each case optionally substituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl or ethoxycarbonyl (which are in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy); propenyloxy, butenyloxy, propinyloxy or butinyloxy (which are optionally substituted by fluorine or chlorine); methylthio, ethylthio., n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio or butinylthio (which are in each case optionally substituted by fluorine or chlorine); methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl (which are in each case optionally substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl, or phenylamino (which are in each case optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl).
Very particularly preferred groups of compounds of the formula (I) are the compounds of the formulae (Ia), (Ib) and (Ic) drawn below 
where
R1, R2 and Z have the meanings indicated above as particularly preferred,
R4 and R5 are identical or different and independently of one another in each case individually represent hydrogen, fluorine, chlorine, methyl or ethylxe2x80x94or in the formula (lb) can also together represent oxygen or sulphurxe2x80x94and
Q represents oxygen, sulphur, N-methyl or N-ethyl.
Z in the general formulae (I) and ((Ia), (Ib) and (Ic) represents in particular the heterocyclic groups listed below 
xe2x80x83where in each case
Q1 represents a group from the series xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, xe2x80x94CH2xe2x80x94, xe2x80x94CH(OH)xe2x80x94, xe2x80x94CHClxe2x80x94, xe2x80x94CHBrxe2x80x94, xe2x80x94C(xe2x95x90CH2)xe2x80x94, xe2x80x94C(xe2x95x90CHF)xe2x80x94, xe2x80x94C(xe2x95x90CF2)xe2x80x94, xe2x80x94C(xe2x95x90CHCl)xe2x80x94, xe2x80x94C(xe2x95x90CHBr)xe2x80x94, xe2x80x94C(xe2x95x90CHOCHF2)xe2x80x94, xe2x80x94C(xe2x95x90CHOCF3)xe2x80x94, xe2x80x94C(xe2x95x90CHOCH2CF3)xe2x80x94,
Q2 represents oxygen, sulphur or a group from the series xe2x80x94COxe2x80x94, xe2x80x94CSxe2x80x94, xe2x80x94CH2xe2x80x94, xe2x80x94CHFxe2x80x94, xe2x80x94CF2xe2x80x94, xe2x80x94CHClxe2x80x94, xe2x80x94CHBrxe2x80x94, xe2x80x94CHOCHF2xe2x80x94, xe2x80x94CHOCF3xe2x80x94, xe2x80x94CHOCH2CF3xe2x80x94,
R6 represents hydrogen, amino, nitro, cyano, carboxyl, carbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl, and
R7 represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- or i-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy,
or where optionally two adjacent groupsxe2x80x94R6 and R6 and R7 and R7 or R6 and R7xe2x80x94together represent in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted alkanediyl or alkenediyl having in each case up to 4 carbon atoms which is optionally interrupted by oxygen, sulphur or a group from the series xe2x80x94SOxe2x80x94, SO2xe2x80x94, xe2x80x94N(CH3)xe2x80x94 or N(C2H5)xe2x80x94 at the beginning (or at the end) or within the hydrocarbon chain.
The definitions of radicals listed above, indicated in general or in ranges of preference, apply both to the end products of the formula (I) and, correspondingly, to the respective starting materials and intermediates required for preparation. These radical definitions can be combined as desired with one another, which therefore includes any desired combinations between the indicated ranges of preferred compounds.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.
Group 1 
In this formula, R1, R2 and R3 have the meanings indicated in the following list:
Group 2 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 3 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 4 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 5 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 6 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 7 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 8 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 9 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 10 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 11 
In this formula, R1, R2and R3 have, for example, the meanings indicated above in Group 1.
Group 12 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 13 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 14 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 15 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 16 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 17 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 18 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 19 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 20 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group, 21 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 22 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 23 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 24 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 25 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 26 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 27 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 28 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 29 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 30 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 31 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 32 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 33 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 34 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 35 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 36 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 37 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 38 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 39 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 40 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 41 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 42 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 43 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 44 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 45 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 46 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 47 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 48 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 49 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 50 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 51 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 52 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 53 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group, 54 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 55 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 56 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 57 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 58 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 59 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 60 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 61 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 62 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 63 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 64 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 65 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 66 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 67 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 68 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 69 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 70 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 71 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 72 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 73 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 74 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 75 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 76 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 77 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 78 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 79 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Table 80 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 81 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 82 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 83 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 84 
In this formula, R1, R2 and R3 have, for example, the meanings indicated above in Group 1.
Group 85 
In this formula, R1, R4 and R5 have the meanings indicated in the following list:
Group 86 
In this formula, R1, R4 and R5 have, for example, the meanings indicated above in Group 85.
Group 87 
In this formula, R1, R4 and R5 have, for example, the meanings indicated above in Group 85.
Group 88 
In this formula, R1, R4 and R5 have, for example, the meanings indicated above in Group 85.
Group 89 
In this formula, R1, R4 and R5 have, for example, the meanings indicated above in Group 85.
Using, for example, 2-(2-fluoro-4-cyano-5-methoxy-phenyl)-4-methyl-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and hydrogen sulphide as starting materials, the course of reaction of the process according to the invention can be illustrated by the following equation: 
A general definition of the substituted aromatic nitriles to be used as starting materials in the process according to the invention for the preparation of the compounds of the general formula (I) is given by the formula (II). In the formula (II), R1, R2, R3 and Z preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I), as preferred or, respectively, as particularly preferred for R1, R2, R3 and Z.
The starting materials of the formula (II) are known and/or can be prepared by known processes (cf. EP-A 370332; DE-A 4238125; DE-A 4303376; U.S. Pat. No. 5084084; Preparation Examples).
Suitable diluents for carrying out the process according to the invention are the customary organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, for example benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, azines, such as pyridine, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water, or pure water.
The process according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. Suitable such auxiliaries are all customary inorganic or organic bases. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, for example sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butylate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
The reaction temperatures when carrying out the process according to the invention can be varied within a relatively large range. It is generally carried out at temperatures between 0xc2x0 C. and 100xc2x0 C., preferably at temperatures between 10xc2x0 C. and 80xc2x0 C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure, generally between 0.1 bar and 10 bar.
To carry out the process according to the invention the starting materials of the formula (II) are introduced, generally in a suitable diluent in the presence of a reaction auxiliary, and the hydrogen sulphide or the thioacetamide is slowly metered in. The hydrogen sulphide or the thioacetamide are preferably employed in a relatively large excess. The reaction mixture is stirred for a number of hours at the particular temperature required. Working up in the process according to the invention is effected in each case in accordance with customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks, and on paths and areas with or without tree stands. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pastures, and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both pre- and post-emergence.
To a certain extent, the compounds of the formula (I) also show a fungicidal action, for example against Pyricularia oryzae in rice.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, axo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, examples being anilides, for example, diflufenican and propanil; arylcarboxylic acids, for example dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, for example 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, for example diclofop(-methyl), fenoxaprop(-ethyl), fluazifop(-butyl), haloxyfop(-methyl) and quizalofop(-ethyl); aznones, for example chloridazon and norflurazon; carabamates, for example chlorpropham, desmedipham, phenmaedipham and propham; chloroacetanilides, for example alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, for example oryzalin, pendimethalin and trifluralin; diphenyl ethers, for example acifluorfen, bifenox, chlormethoxynil (X-52), chlornitrofen, fluoroglycofen, fomesafen, halosafen, lactofen, nitrofen and oxyfluorfen; ureas, for example chlortoluron, cumyluron (JC-940), diuron, dymron (daimuron), fluormeturon, isoproturon, linuron and methabenzthiazuron; hyroxylamines, for example alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, for example imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, for example bromoxynil, dichlobenil and ioxynil; oxyacetamides, for example mefenacet; sulphonylureas, for example AC-014 (AC-322140), amidosulfuron, bensulfuron(-methyl), chlorimuron(-ethyl), chlorsulfuron, cinosulfuron, DPX-47, HOE-404, imazosulfuron, metsulfuron(-methyl), nicosulfuron, primisulfuron, pyrazosulfuron(-ethyl), thifensulfuron(-methyl), triasulfuron and tribenuron(-methyl); thiocarbamates, for example butylate, cycloate, diallate, dimepiperate, EPTC, esprocarb, molinate, prosulphocarb, thiobencarb (benthiocarb) and triallate; triazines, for example atrazine, cyanazine, dimethametryn, prometryne, simazin, simetryne, terbutryne and terbutylazin; triazinones, for example hexazinon, metamitron and metribuzin; others, for example aminotriazole, benfuresate, bensulide, bentazone, benzofenap, bromobutide, butamifos, cafenstrole (CH-900), cinmethylin, clomazone, clomeprop, clopyralid, DEH-112, difenzoquat, dimethenamid, dithiopyr, ethofumesate, flumetsulam, fluorochloridone, glufosinate, glyphosate, amiprophos(-methyl), anilofos, etobenzanid (HW-52), isoxaben, KPP-314, KUH-833, KUH-911, KUH-920, MK-243, naproanilide, NSK-850, oxadiazon, piperophos, propanil, pyrazolate, pyrazoxyfen, pyributicarb, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or spreading.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 10 g and 10 kg of active compound per hectare of soil surface, preferably between 50 g and 5 kg per ha.